JP2000052490A - Laminated cylindrical body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide properties capable of withstanding a long-term use even in a metal corrosive liquid by providing an cylindrical vinylester resin layer, which is made of a material excellent in heat conductivity and contains carbon fiber on a surface at least contacting with the metal corrosive liquid. SOLUTION: A carbon fiber reinforced resin essentially consisting of a vinylester resin and carbon fiber as main components is laminated on the inner surface and/or outer surface of a metal pipe. The metal having a heat conductivity of 100-450 w/mK is used, and, more particularly, may be copper, aluminum, and an alloy thereof. Acid is normally used for the metal corrosive liquid where a heat exchanging annular body, and more particularly, hydrochloric acid, sulfuric acid, nitric acid and a mixed acid thereof or the like may be used. As a vinylester resin, an epoxy acrylate resin may be used, which is normally obtained by the reaction between an epoxy resin and an unsaturated nonobasic acid. An example of the unsaturated monobasic acid may be an acrylic acid, a methacrylic acid or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Industrial application] Adjusts the temperature of metal corrosive liquids used for removing oxide films and dirt adhering to metals after heat treatment, and for cleaning metal parts with resin, ink, etc.
The present invention relates to a laminated tube used for control.

[0002]

2. Description of the Related Art Conventionally, a heat-treated metal is immersed in a metal corrosive liquid such as an acid in order to remove an adhered oxide film and dirt. When a metal is immersed in a metal corrosive liquid such as an acid, heat is generated by an oxidation reaction, and the liquid temperature rises. When the liquid temperature rises, the reaction proceeds excessively and invades the base material.On the other hand, when the liquid temperature decreases, it takes a long time to perform a predetermined process and lowers productivity. Because of the necessity, the washing operation was interrupted when the temperature of the solution rose, and the solution was naturally cooled.

[0003]

Therefore, a heat exchange tube is placed in a container containing a metal corrosive liquid.
There is a method to control the temperature of the metal corrosive liquid by flowing a heat medium such as water into the tube, but the heat exchange tube uses a heat transfer material such as copper or aluminum to transfer the temperature efficiently. It was made of a high rate metal material. However, these metallic materials corrode themselves in a metal corrosive liquid, and could not be used for a long period of time, at most for only a few days.

Therefore, a heat exchange tube made of a material which is not corroded by a metal corrosive liquid such as titanium can be used for a long period of time. However, its heat conductivity is higher than that of aluminum or copper. As a result, it was inferior by several steps, and the number of heat exchange tubes had to be increased, and the temperature could not be controlled sufficiently with the same size and number of tubes as before. An object of the present invention is to provide a laminated tubular body for heat exchange that can withstand long-term use even in a metal corrosive liquid and has a sufficient thermal conductivity.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and have found that at least a cylindrical body made of a material having good thermal conductivity, such as copper or aluminum, has a metal corrosive liquid. By providing a vinyl ester resin layer containing carbon fibers on the surface that comes in contact with, it has been found that a heat exchange tubular body that can withstand long-term use can be obtained without impairing the thermal conductivity, and reached the present invention. . That is, the gist of the present invention is to provide a laminated tubular body for a metal corrosive liquid, wherein a carbon fiber reinforced resin containing vinyl ester resin and carbon fiber as main components is laminated on the inner surface and / or outer surface of the metal tube. Exists.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the liquid for metal corrosion in which the heat exchange tubular body of the present invention is used, an acid is usually used. Specifically, hydrochloric acid, sulfuric acid,
Nitric acid and mixed acids thereof. The heat exchange tubular body of the present invention is formed by laminating a carbon fiber reinforced resin containing vinyl ester resin and carbon fiber as main components on an inner surface and / or an outer surface of a metal tube. Preferably, the surface of the laminated tubular body that contacts the metal corrosive liquid is made of carbon fiber reinforced resin. More preferably, it is obtained by laminating a carbon fiber reinforced resin on the outer surface of the metal tube.

As a metal, the thermal conductivity is 100 to 450.
W / mK is used, and specific examples include copper, aluminum, and alloys containing these. From the viewpoint of economy, a material having a heat conductivity of less than 100 W / mK may be used, but the effect of heat transfer is reduced and a heat transfer area needs to be taken. The size of the metal tube depends on the size of the container containing the metal corrosive liquid, but the outer diameter is
It is usually 5 to 300 mm, preferably 10 to 200 mm. When the outer diameter is smaller than 5 mm, the number of tubular bodies increases to secure a predetermined heat transfer area, or the pressure loss increases, which is not preferable. On the other hand, if it is larger than 300 mm, the efficiency of heat transfer is reduced. Length is usually 100-5000m
m, the thickness of the tube is usually 0.5 to 10 mm, preferably 2 to 10 mm.
６6 mm. If the thickness of the tube is smaller than 0.5 mm, the strength of the heat exchange tubular body becomes insufficient, while if it is larger than 10 mm, the heat transfer coefficient becomes small. By using the metal tube, the strength that was insufficient with only the carbon fiber reinforced resin can be compensated, and further, the workability of the joint portion can be ensured.

[0008] As the vinyl ester resin, an epoxy acrylate resin is used and is usually obtained by reacting an epoxy resin with an unsaturated-basic acid. Examples of the epoxy resin as a raw material of the vinyl ester resin include a bisphenol type epoxy resin and a novolak type epoxy resin. Representative examples of the unsaturated-basic acid include acrylic acid, methacrylic acid, crotonic acid, monomethylmalate, monopropylmalate, sorbic acid and mono (2-ethylhexyl) malate.

The vinyl ester resin usually contains a polymerizable unsaturated monomer. The polymerizable unsaturated monomer component forms a skeleton of a cured product by polymerization, and examples thereof include aromatic monomers such as alkyl acrylate, methacrylic ester, styrene, and vinyl toluene, and monomers such as acrylritrile. In addition to these monomers, if necessary, monomers that contribute to the formation of a crosslinked structure such as divinylbenzene, diallyl phthalate, and ethylene glycol dimethacrylate can be used. Among these monomers, the use of aromatic monomers, particularly styrene, is preferable in terms of cost and low cost, good compatibility with other components, and contribution to improving the water resistance of the composite material after curing. .

[0010] Further, vinyl ester resins are usually
The radical polymerization initiator is blended immediately before use. As the radical polymerization initiator, an organic peroxide is used, and specific examples thereof include ketone peroxide, peroxyketal, hydroperoxide, diacyl peroxide, peroxyester, and peroxydicarbonate. One.

The vinyl ester resin has good adhesion to carbon fibers and metals, and can prevent voids and peeling. In addition, because it has corrosion resistance and can be cured at room temperature or light,
No large-scale equipment is required. As the carbon fiber, either a long fiber or a short fiber can be used, and the carbon fiber is a woven fabric obtained by plain weaving the long fiber, a prepreg obtained by aligning the carbon fiber of the long fiber in one direction, or a short fiber. It may be a sheet made of carbon fibers such as a hardened mat or a tow in which several long fibers are bundled with a bundle. The use of long fibers improves the heat transfer coefficient, and can be easily wound around the tubular body, and the long fibers can improve the strength of the tubular body.
preferable.

The diameter of the carbon fiber is usually 5 to 15 μm, and the thermal conductivity is usually 100 w / mk or more, preferably 100 w / mk or more.
Ｗ1500 w / mk. Thermal conductivity of carbon fiber is 10
If it is less than 0 w / mk, the heat transfer coefficient becomes small, which is not preferable. In the case of woven fabric, the basis weight is usually 30 to 1000 g / m.
² , preferably 100 to 600 g / m ² . If the basis weight is less than 30 g / m ^2, it must be laminated in multiple layers to obtain a predetermined thickness, and there is a problem in productivity.
If it is larger than / m ^2, it is not suitable because it is difficult to impregnate the resin and it is easy to cause defects such as voids and pinholes.

The proportion of carbon fibers in the carbon fiber reinforced resin layer is usually 30 to 70% by weight, preferably 40 to 60% by weight.
% By weight. The proportion of the vinyl ester resin is usually 30 to 70% by weight, preferably 40 to 60% by weight. If the proportion of the carbon fibers is too small, sufficient thermal conductivity cannot be obtained. If the proportion of the carbon fibers is too large, voids are formed in the carbon fiber reinforced resin layer, and a metal corrosive liquid may enter the voids and corrode the surface of the metal tubular body.

The thickness of the carbon fiber reinforced resin layer is usually 0.1
10 to 10 mm, preferably 0.5 to 5 mm. When the thickness is less than 0.1 mm, there is little time margin for diffusion of the liquid in the resin, and there is a problem in durability. When the thickness is more than 10 mm, the heat transfer coefficient of the resin layer becomes small and the ability as a heat exchanger becomes low. . As a method of manufacturing the carbon fiber reinforced resin layer, a vinyl ester resin mixed with short fibers of carbon fiber may be applied to the surface of the metal tubular body, or a sheet-like carbon fiber may be attached using the vinyl ester resin, A continuous long fiber tow may be wound.

When a sheet-like carbon fiber is used, usually, first, a vinyl ester resin is applied to the surface of the metal tubular body so as to have a thickness of 0.02 to 0.5 mm.
Then, when using a carbon fiber sheet, the carbon fiber sheet is wound around a metal tubular body, and a vinyl ester resin containing a curing agent is further applied thereon, and the vinyl ester resin is applied to the carbon fiber sheet with a spatula or the like. Impregnate uniformly and avoid voids. In addition, it is preferable that the carbon fiber sheet is wound a plurality of times from the viewpoint that a defect due to an end joint portion of the carbon fiber sheet can be covered.

When using carbon fiber tow, usually, first, a vinyl ester resin is applied to the surface of the metal tubular body, and then the tow is wound tightly while supplying the vinyl ester resin. When long fibers are used, it is preferable to arrange the carbon fibers so that at least a part thereof is along the circumferential direction of the tube or to use a woven fabric, since heat exchange efficiency becomes good. Particularly preferred is a material having a high thermal conductivity without defects such as peeling from a metal tubular body since the fabric can be wound by applying a moderate tension by using the fabric and the fibers are oriented in the thickness direction by the weave of the fabric. Can be tested.

The tubular body obtained in this manner is connected, if necessary, to a resin tube for flowing a heat medium such as cooling water or hot water through the inside of the tubular body at both ends. The members are connected by means such as welding or bonding. If the connecting member is made of a material that is corroded by acid,
It is desirable to provide a carbon fiber reinforced resin layer on a portion of the outer surface of the connecting member that contacts the acid.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A connecting member is welded to both ends so that a resin tube can be attached. The outer diameter is 80 mm and the thickness is 2 m.
A sheet (dialead FP35-220 manufactured by Mitsubishi Chemical Corporation) in which a carbon fiber having a fiber diameter of 10 μm and a thermal conductivity of 140 W / mk is plain woven in a copper tube having a length of 1000 mm and a thermal conductivity of 380 W / mk. Vinyl ester resin (Ripoxy R-802 manufactured by Showa Polymer Co., Ltd.) which is a bisphenol A type epoxy acrylate of room temperature curing type and methyl ethyl ketone peroxide (Permec N manufactured by NOF Corporation)
While being impregnated with the mixture, the copper tube was wound three times around the outer periphery of the copper tube and cured to obtain a heat exchange tubular body. The carbon fiber ratio of the obtained carbon fiber reinforced resin was 50% by weight, and the thickness of the carbon fiber reinforced resin layer was 0.9 mm. Similarly to the outer periphery of the copper tube, three layers of carbon fiber sheets were laminated using a vinyl ester resin also on a portion of the connection member that contacts the acid. A connecting member was welded to both ends of the obtained tubular body, a resin tube was attached via the connecting member, and cooling water was allowed to flow inside the tubular body. Even if this tubular body is immersed in an acid, there is no corrosion due to the acid, and the temperature rise of the acid can be effectively suppressed.

[0019]

According to the present invention, a tubular body for a metal corrosive liquid having excellent strength, thermal conductivity and corrosion resistance can be obtained.

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AA37A AA37C AB01B AB17 AK21A AK21C BA03 BA06 BA08 BA10A BA10C DA11 DG01A DG01C DG03A DG03C DG04A DG04C DG12A DG12C DH01A DH01J 002 BG04X BG05X BG10X CD20W DA016 FA046 GF00

Claims (9)

[Claims] 1. A laminated tubular body for a metal corrosive liquid, wherein a carbon fiber reinforced resin containing a vinyl ester resin and carbon fibers is laminated on an inner surface and / or an outer surface of a metal tube. 2. The thermal conductivity of the metal is 100 to 450 W / mk.
The laminated tubular body according to claim 1, which is: 3. The thickness of the carbon fiber reinforced resin layer is 0.1 to 10
3. The laminated tubular body according to claim 1, wherein 4. The laminated tubular body according to claim 1, wherein the thermal conductivity of the carbon fiber is 100 W / mK or more. 5. The carbon fiber according to claim 1, wherein the carbon fiber is a woven fabric, a prepreg obtained by aligning long fibers, or a mat comprising short fibers.
5. The laminated tubular body according to any one of items 4 to 4. 6. The carbon fiber according to claim 1, wherein the carbon fiber is a long fiber.
A laminated tubular body according to any one of the preceding claims. 7. The laminated tubular body according to claim 1, wherein the longitudinal direction of the carbon fibers is the circumferential direction of the heat exchange tubular body. 8. The laminated tubular body according to claim 1, wherein the laminated tubular body is used for controlling the temperature of a metal corrosive liquid. 9. A laminated tubular body formed by laminating a carbon fiber reinforced resin containing a vinyl ester resin and carbon fibers on the inner surface and / or outer surface of a metal tube.